Easily cleanable polymer laminates

ABSTRACT

A substrate having an adherent and stain resistant layer having durability and flexibility, said layer comprising the reaction product of a reactive polyester having free carboxylic acid and/or hydroxyl groups, a hydroxyl terminated polymer including repeat units from an oxetane having pendant -CH2-O-(CH2)n-Rf groups (said Rf groups generally being a fluorinated alkyl group) and an amino resin curative. The substrate may be printed or embossed or both. The coated substrate has both stain resistant properties and dry erase properties with dry erase markers. The coated substrate can be used as prepared or applied to other substrates.

This application is a continuation-in-part of prior application Ser. No.09/035,595, filed Mar. 05, 1998, abandoned, entitled Easily CleanablePolymer Laminates, which is herein incorporated by reference.

FIELD OF INVENTION

This invention relates to laminates having improved stain resistance dueto the incorporation of a polymer having repeat units from an oxetanemonomer having pendant fluorinated groups into a stain resistant surfacelayer. The stain resistant layer can also be adhered to a variety ofsubstrates including polyesters, paper, polyolefins etc. The coatingsexhibit dry erase characteristics when dry erase markers are used.

BACKGROUND OF INVENTION

U.S. Pat. No. 4,603,074 sets forth a polyester-amino resin compositionthat can form a stain resistant layer on plasticized polyvinyl chloridesubstrates. While this coating was very good with respect to stainresistance and abrasion resistance, it would be desirable to havefurther increases in cleanability without using solvents, whilemaintaining stain resistance and abrasion resistance.

A variety of polymeric coatings and surface treatments for natural andsynthetic materials have been developed to enhance the dirt and stainrelease characteristics. Some of the more effective ones to date allowfor reapplication of the anti-soil treatment after cleaning (such aswith carpets) or in tents.

Dry erase boards and ink or marker pens are popular replacements forchalkboards. A variety of relatively nonporous writing surfaces havebeen developed along with special dry erase markers that are speciallydesigned to leave strong well defined continuous marks that can beerased with a dry cloth or eraser. U.S. Pat. Nos. 3,834,823; 3,922,457;3,949,132; 4,746,576; 4,988,123 and 5,324,764; disclose such technologyand are herein incorporated by reference for their teachings on dryerase systems.

U.S. Pat. No. 5,650,483 describes the preparation of oxetane monomersuseful to form oxetane polymers with pendant fluorinated chains. Theoxetane polymers were characterized as having low surface energy, highhydrophobicity, and a low coefficient of friction. That patent isincorporated by reference herein for its teachings on how to prepare theoxetane monomers and polymers. In the reference the oxetane polymerscould be formulated with isocyanates to form crosslinked compositions.Additional patents issued on variations of the oxetane monomers andpolymers. These were U.S. Pat. Nos. 5,654,450; 5,663,289; 5,668,250, and5,668,251 also incorporated herein by reference.

SUMMARY OF INVENTION

According to the present invention, an improved stain and abrasionresistant polymeric layer was developed by incorporating a minor amountof a hydroxyl terminated polymer having repeat units from an oxetanemonomer having pendant fluorinated groups thereon into a polyester-aminoresin composition. The hydroxyl terminated polymer may have other repeatunits such as derived from the ring opening polymerization of cyclicethers including tetrahydrofuran and/or more conventional ring openingpolymerization of oxetane or epoxy monomers. Excellent stain release andabrasion release are observed with as little as 0.1, 0.2 or 0.5 to 10 or15 parts by weight of repeat units from the oxetane monomer with pendantfluorocarbon groups based on 100 parts of polyester resin and aminoresin in the dry coating. The coating may be as thin as 0.1 to 2 or 4mil (thousandths of an inch) thick. One preferred embodiment is a layerof a flexible vinyl chloride polymer coated with said polyester-aminoresin composition in solvent and heated to cure and adhere the resin tothe vinyl chloride polymer layer with removal of the solvent. Thisprovides the flexible vinyl chloride polymer layer with a coating whichis stain resistant or which can readily be cleaned (either dry or withsolvent) without significant abrasion to remove stains.

The vinyl chloride layer may be a vinyl chloride polymer, which is aplastisol coated and fused or is a plasticized vinyl chloride polymercomposition which has been calendered or extruded. The vinyl chloridemay be applied to a backing, substrate or support. In either case thepolyvinyl chloride layer (about 1 to 30 or 100 mils thick) can beprinted one or more times. The printed layer can be embossed, beforeand/or after printing, and finally coated with a layer of a solution ofa said polyester-amino resin composition and cured to provide the vinylchloride polymer layer with an outer stain resistant layer about 0.1 to2 or 4 mils or more thick.

DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS

The reactive polyester-amino resin for use as the outer or top coatingon a substrate is prepared from a solution of a reactive polyester(alkyd resin) and an amino resin in a solvent (such as methyl ethylketone, water, alcohols, or combination thereof) containing a catalystsuch as p-toluene sulfonic acid and is applied at a temperaturedesirably of at least about 150, 200, 250, or 400° F. or more (66, 93,121, or 204° C.) to cause curing or cross-linking of the polyester resinand the amino resin. The reactive polyester-amino resin composition maybe applied to a substrate (e.g. vinyl chloride polymer, polyester,cellulosic, polyolefin composition) directly or with an intermediate tielayer. The substrate may be with or without a backing or substrate, withor without the printing and with or without the embossing. A preferredembodiment includes the catalyzed reactive polyester-amino resinsolution being applied over a tie layer to an embossed and printedcompounded and plasticized vinyl chloride polymer composition carried ona suitable backing or substrate. Such vinyl chloride polymer basedsubstrates are readily available from wallcovering manufacturers.

The polyester resins (alkyd resins) are made by a condensationpolymerization reaction, usually with heat in the presence of acatalyst, or a mixture of a polybasic acid and a polyhydic alcohol.Fatty monobasic oils or fatty acids, monohydroxy alcohols and anhydridesmay be present. The polyester contains active hydrogen atoms, e.g.,carboxylic acid groups and/or hydroxyl groups for reaction with theamino resin. Example of some acids to use to form the alkyd resin orreactive polyester are adipic acid, azelaic acid, sebacic acid,terephthalic acid, phthalic anhydride, and so forth. Examples of somepolybasic alcohols include ethylene glycol, propylene glycol, diethylene3 glycol, dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane and thelike. Mixtures of the polyols and polycarboxylic acids can be used. Anexample of a suitable reactive polyester is the condensation product oftrimethylol propane, 2,2-dimethyl-1,3-propanediol,1,4-cyclohexanedimethanol, phthalic anhydride and adipic acid. Mixturesof these reactive polyester or alkyd resins can be used. Alkyd resinsare well known as shown by the “Encyclopedia of Polymer Science andTechnology,” Vol. 1, 1964, John Wiley & Sons, Inc., pages 663-734;“Alkyd Resins,” Martens, Reinhold Publishing Corporation, New York, 1961and “Alkyd Resin Technology,” Patton, Interscience Publishers, adivision of John Wiley and Sons, New York, 1962. Some unsaturatedpolybasic acids and unsaturated polyols may be used in the condensationreaction but are generally undesirable. The reactive polyester (alkydresin) is usually added to the amino resin while dissolved or suspendedin a solvent, e.g. such as a mixture of polyester in a ketone and analkyl acetate at about 60-80% solids or a mixture of polyester in alkylalcohols and alkylene glycol alkyl ethers.

Alternatively to using a separate polyester and hydroxyl terminatedpolymer including repeat units from an oxetane monomer having a pendantpendant —CH₂—O—(CH₂)_(n)—Rf one can react said hydroxyl terminatedpolymer into the polyester thus replacing two components with a singlecomponent. The hydroxyl terminated polymer is more completely bound intothe network as a result of prereacting the polyester forming componentswith the hydroxyl terminated polymer and is therefore less likely to beremoved from the coating by wear or cleaning. In the claims thepolyester including the repeat units derived from copolymerizing saidhydroxyl terminated polymer into said polyester is described as areactive polyester resin including therein at least one repeat unitderived from copolymerizing into said polyester a hydroxyl terminatedpolymer including repeat units from an oxetane having a pendant—CH₂—O—(CH₂)_(n)—Rf group. One skilled in the art would be able tooptimize reaction conditions for forming such a polyester such that theoxetane repeat units are incorporated into the polyester. Such reactionconditions may include prereaction of the dibasic acid and the oxetanepolymer having a pendant —CH₂—O—(CH₂)_(n)—Rf in a separate reaction andthen adding the remaining diacids and polyols to complete thepolymerization of the polyester.

The amino resin to be reacted with the reactive polyester is analkylated benzoguanamine-formaldehyde, an alkylated urea-formaldehydeor, preferably, an alkylated melamine-formaldehyde resin. Mixtures ofthese resins can be used. The alcohol used to modify thebenzoguanamine-formaldehyde, urea-formaldehyde or melamine-formaldehyderesin can be n-butanol, n-propanol, isopropanol, ethanol or methanol andso forth. These amino resins are well known and include those set forthin “Aminoplastics,” Vale et al, lliffe Books Ltd., London, 1964; “AminoResins,” Blair, Reinhold Publishing Corporation, New York, 1959, “ModernPlastics Encyclopedia 1980-1981,” pages 15, 16 and 25 and “Encyclopediaof Polymer Science And Technology,” John Wiley & Sons, Inc., Vol. 2,1965, pages 1 to 94.

Sufficient amounts by weight of the reactive polyester and amino resinare employed to provide a stain resistant, layer having good durabilityand flexibility and having good adhesion to the substrate. Thesematerials are desirably cured at temperatures of at least 150, 200, 250or 400° F. or more (66, 93, 121, or 204° C.) for effective times in thepresence of a minor amount by weight of an acidic catalyst such as boricacid, phosphoric acid, acid sulfates, hydrochlorides, phthalic anhydrideor acid, oxalic acid or its ammonium salts, sodium or barium ethylsulfates, aliphatic or aromatic sulfonic acids such as p-toluenesulfonic acid (preferred), methane sulfonic acid and the like. It isimportant that the stain resistance imparted by the polyester and aminoresin be optimized by controlling things such as glass transitiontemperature, crosslink density and the presence of molecules that mayact as plasticizers or other molecules that may transport or attractstaining molecules in the coating. Prior to curing flatting agents orother additives can be added to the mixture of the reactive polyesterand amino resin.

The hydroxyl terminated polymer(s) including repeat units from anoxetane having a pendant —CH₂—O—(CH₂)_(n)—Rf group are prepared. Thesecan be prepared according to the teachings of U.S. Pat. Nos. 5,650,483;5,668,250 and 5,663,289 hereby incorporated by reference for thoseteachings. The oxetane monomer desirably has the structure

wherein n is an integer from 1 to 3 and Rf, independently, on eachmonomer is a linear on branch alkyl group of 1 to 20 carbon atoms with aminimum of 25, 50 or 75 percent of the H atoms of said Rf being replacedby F and optionally up to all of the remaining H atoms being replaced byl, Cl or Br, or each Rf, independently, being an oxaperfluorinatedpolyether having from 4 to 60 carbon atoms; R being H or an alkyl of 1to 6 carbon atoms; preferably Rf has at least 85 and more preferably atleast 95% of said H atoms replaced by F. Preferably said linear orbranched alkyl group is of from 1 or 3 to 7 or 10 carbon atoms.

The repeat units from said oxetane monomers desirably have the structure

where n, Rf, and R are as described above.

The hydroxyl terminated polymer(s) including repeat units from saidoxetane monomers can have one or more terminal hydroxyl groups. Theydesirably have number average molecular weights from about 250; 500;1,000 or 5,000 to about 50,000 or 100,000. The polymer(s) can be ahomopolymer or a copolymer of two or more different oxetane monomers.The polymer may also be a copolymer of cyclic ether molecules havingfrom 2 to 4 carbon atoms in the ring such as tetrahydrofuran and one ormore oxetane monomers as described in the previously incorporated U.S.Pat No. 5,668,250. The copolymer may also include copolymerizablesubstituted cyclic ethers such as substituted tetrahydrofurans. Therepeat unit from a tetrahydrofuran monomer has the formula to—(O—CH₂—CH₂—CH₂—CH₂—). The hydroxyl terminated polymer(s) optionallyincludes a cyclic tetramer of said oxetane monomer, which may be abyproduct of the polymerization. In some embodiments, said hydroxylterminated polymer includes up to 10, 20, or 30 wt % of said tetramerbased on the weight of said hydroxyl terminated polymer(s).

It is desirable that the polymer including repeat units from an oxetanehaving a pendant —CH₂—O—(CH₂)_(n)—Rf group has one or more hydroxylgroup in that this provides a possible mechanism for this polymer to bechemically bound into the polyester-amino resin composition. It isacknowledged that the amount of such bound polymer has not been measuredin the examples and it may be a small or large percentage of the totalpolymer with said oxetane repeat units. In some embodiments it may bedesirable to prereact the hydroxyl terminated polymer with the polyestercomponent to increase the percentage of hydroxyl polymer bound into thecoating. It is also acknowledged that the percentage of the polymer withsaid oxetane repeat units and the oxetane repeat units themselves maynot be uniformly distributed through the bulk of the coating. Saidoxetane repeat units may be disproportionately present at the surface ofthe coating due to the low surface tension of those repeat units.

The amount of the various components in the coating will be generallyspecified in relationship to 100 parts by weight of the polyester resinand the amino resin crosslinking agent. The weight ratio of polyesterresin (neat) to amino resin (neat) can vary widely but desirably is fromabout 10:90 to 90:10 and more desirably from about 20:80 to 80:20.Generally it is more desirable to match the moles of reactive groups onthe polyester to within 10 to 20% to the number of moles of reactivegroups on the amino resin. The number of moles of reactive groups can bedetermined by dividing the weight of the component by the equivalentweight for the component. The term “neat” after polyester and aminoresin does not exclude using polyesters and amino resins that arereceived dissolved in solvents but rather specifies that the amount usedis to be recalculated based on the weight without the solvent. For thepurposes of this disclosure no distinction will be made whether theamino resin crosslinks the polyester resin or visa versa.

The amount of carriers and/or solvent(s) in the coating composition canvary widely depending on the coating viscosity desired for applicationpurposes, and solubility of the components in the solvent. Thesolvent(s) can be any conventional solvent for polyester-amino resinsystems. These carriers and/or solvents include but are not limited towater, alkyl alcohols of 1 to 10 carbon atoms, ketones of from 3 to 15carbon atoms e.g. methyl ethyl ketone or methyl isobutyl ketone,alkylene glycols and/or alkylene glycol alkyl ethers having from 3 to 20carbon atoms, acetates and their derivatives, ethylene carbonate, etc.Illustrative U.S. patents of the carrier and/or solvent systemsavailable include U.S. Pat. Nos. 4,603,074; 4,478,907; 4,888,381 and5,374,691 hereby incorporated by reference for their teachings both ofcarriers and/or solvent systems and of polyesters and amino resins. Theamount of solvent(s) can desirably vary from about 20 parts by weight toabout 400 parts by weight per 100 parts by weight of total polyesterresin and amino resin.

The amount of the oxetane repeat units having a pendantCH₂—O—(CH₂)_(n)Rf group is desirably from about 0.1 or 0.2 to about 10or 15 parts by weight and more desirably from about 0.5 to about 10 or15 parts by weight per 100 parts total weight of said polyester resinand amino resin. Of course if the hydroxyl terminated polymer(s)including repeat units from said oxetane has a significant amount ofrepeat units from tetrahydrofuran or other repeating unit therein, thehydroxyl terminated polymer's weight will exceed that of said oxetanerepeat units.

The amount of catalyst is an amount that effectively catalyzes themutual crosslinking of the polyester and amino resins under thecrosslinking conditions chosen (usually elevated temperatures). As thecrosslinking temperature increases above 150, 200, 250, or 400° F. (66,93, 121, or 204° C.) the amount of catalyst can be reduced. Effectiveamounts of catalyst can vary from about 0.1, 0.5 or 1 to about 6 or 8parts by weight and preferably from about 2 or 3 to about 6 parts byweight per 100 parts by weight total of said polyester and amino resins.

Conventional flattening agents can be used in the coating composition inconventional amounts to control the gloss of the coating surface to anacceptable value. Examples of conventional flattening agents include thevarious waxes, silicas, aluminum oxide, alpha silica carbide, etc.Amounts desirably vary from about 0 or 0.1 to about 5 or 10 parts byweight per 100 parts by weight total of said polyester and amino resins.For most embodiments high gloss is preferred.

Additionally other conventional additives for polyester and amino resincompositions or for other clear coating applications in general can beused in the composition. Examples include viscosity modifiers,antioxidants, antiozonants, processing aids, pigments, fillers,ultraviolet light absorbers, adhesion promoters, emulsifiers,dispersants, etc.

While this disclosure generally teaches applying the dry-erase coatingdirectly to a substrate, it also provides for intermediate coating(s)between the substrate and the dry erase coating. These intermediatecoating(s) can be decorative coatings to provide a colored background ora printed (patterned) background. Alternatively or additionally they canbe a buffer between the substrate and the dry-erase coating preventinginteraction between the dry-erase coating and the substrate. Or they canprevent interaction between components in the substrate and componentsin the dry-erase coating (e.g. keeping plasticizer from the substratefrom migrating into the coating). An intermediate coating(s) may alsofunction to improve adhesion of the dry erase coating to the substratewhen adhesion is a concern. An example where adhesion might be improvedis with a polyolefin (polyethylene or polypropylene) substrate which maybe plasma or corona surface treated or have a hydrocarbon intermediateadhesive layer applied thereto before the dry-erase coating is applied.

The substrates may be any material which would benefit from a stainresistance or dry-erase coating. Examples include cellulosic products(coated and uncoated paper, boardstock, cardboard, wood and paneling),fibers, synthetic polymers (including polyolefins, polyesters,polycarbonates, polystyrene, poly (methacrylates) and especially highlyfilled or highly plasticized ones which are more permeable towardsstains e.g. polyvinyl chloride), metals (requiring temporary orpermanent protection from stains), and ceramics.

The coating composition can be prepared by a variety of mixingtechniques. Most of the components can be prediluted or precombined withother components. When the catalyst, polyester resin, and amino resinare combined, they can begin to crosslink. A convenient formulationprocedure is to combine the polyester resin, solvent(s), amino resin,and any non catalyst additives in one container. In a separate containerthe catalyst and optionally solvent can be stored. Shortly beforeapplication the catalyst can be combined and mixed with the othercomponents.

The substrate with stain resistant layers of the present invention reparticularly useful as dry erase writing surfaces (including boards,posters, papers, clipboards, menus, etc.) wallcoverings, anti graffitisurfaces e.g. in public areas including restrooms, and in kitchens andfood preparation areas. However, these stain resistant laminates, also,can be used in the manufacture of tablecloths, shoe uppers, luggageexteriors, upholstery, vehicle interiors and seats, golf bags and othersporting goods and so forth.

The polyvinyl chloride can be an emulsion (plastisol grade) or asuspension grade vinyl chloride polymer. The vinyl chloride polymer canbe polyvinyl chloride homopolymer (preferred) or a copolymer of a majoramount by weight of repeat units from vinyl chloride and a minor amountby weight from a copolymerizable monomer selected from the groupconsisting of vinyl acetate, vinylidene chloride and maleic ester. Bulkand solution vinyl chloride polymers, also may be used. Mixtures ofvinyl chloride polymers can be used. Vinyl chloride polymers andcopolymers are well known and include those set forth in “Vinyl andRelated Polymers,” Schildknecht, John Wiley & Sons, Inc., New York,1952; Sarvetnick, “Polyvinyl Chloride,” Van Nostrand Reinhold Company,New York 1969; Sarvetnick, “Plastisols and Organosols,” Van NostrandReinhold Company, New York, 1972 and “Modern Plastics Encyclopedia1980-1981,” October, 1980, Volume 57, No. 10A, McGraw-Hill Inc., NewYork.

The amount of plasticizer used to plasticize the vinyl chloride polymerto make it flexible may vary from about 20 or 30 to about 100 parts byweight per 100 parts by weight of total vinyl chloride polymer resinmore desirably from about 20 or 30 to about 50 or 60 parts by weight forwallpaper applications and from about 60 to about 100 parts by weightfor upholstery type applications per 100 parts by weight of totalpolyvinyl chloride. Any conventional plasticizer for PVC can be used.Examples of plasticizers which may be used are butyl octyl phthalate,dioctyl phthalate, hexyl decyl phthalate, dihexyl phthalate, diisooctylphthalate, dicapryl adipate, dioctyl sebacate, trioctyl trimellitate,triisooctyl trimellitate, triisononyl trimellitate, isodecyl diphenylphosphate, tricresyl phosphate, cresyl diphenyl phosphate, polymericplasticizers, epoxidized soybean oil, octyl epoxy tallate, isooctylepoxy tallate and so forth. Mixtures of plasticizers may be used.

Other vinyl chloride polymer compounding ingredients are desirablyincorporated in the vinyl chloride polymer compositions. Examples ofsuch ingredients are the silicas such as precipitated silica, fumedcolloidal silica, calcium silicate and the like, calcium carbonate,ultra violet light absorbers, fungicides, carbon black, barytes,barium-cadmium-zinc stabilizers, barium-cadmium stabilizers, tinstabilizers, dibasic lead phosphite, Sb₂O₃, zinc borate, molybdates suchas ammonium octa-molybdates, aluminum oxide, aluminum trihydrate and soforth and mixtures of the same. TiO₂, red iron oxide, phthalocyanineblue or green or other color pigments can be used. The pigments and theother dry additives preferably are dispersed or dissolved in one or moreplasticizers before adding to the plasticized vinyl chloride polymercompositions. These compounding ingredients are used in effectiveamounts by weight to control color, mildew, stabilization toultra-violet light and heat, viscosity and so forth of the plasticizedvinyl chloride polymer.

The vinyl chloride polymer composition may contain suitable blowing orfoaming agents such as sodium bicarbonate, and the organic agents like1,1-azobisformamide, 4,4-oxybis (benzene sulfonylhydrazide),p-toluenesulfonyl hydrazide, or water and so forth to form a cellular orfoamed vinyl chloride polymer composition layer or sheet on fusing. Theblowing agents may require an activator. Such blowing agents are wellknown.

Vinyl chloride polymer blending or extender resins, also, can be used inthe compositions in a minor amount by weight as compared to the vinylchloride polymer composition.

The ingredients forming the vinyl chloride polymer composition may becharged to and mixed together in any one of several mixing devices suchas a Ross Planetary mixer, Hobart dough type mixer, Banbury, 2-rollrubber mill, Nauta mixer and ribbon blender and so forth.

The vinyl chloride polymer composition can be formed into layers offilms, which can be unsupported or supported (preferred). Where a vinylchloride polymer plastisol composition is used, it may be cast on arelease surface and heated to fuse it to form a film. Where aplasticized suspension grade vinyl chloride polymer composition is used,it can be calendered or extruded and fused to form a film. Temperaturesmay vary from about 200 to about 400° F. (93-204° C.). However, it ispreferred that in either case the compounded vinyl chloride polymercompositions be supported or have a backing. In the case of thesupported vinyl chloride polymer composition, the substrate can be awoven fabric (drill, scrim, cheesecloth, and so forth), a knit fabric, anon-woven fabric, paper etc. The fabric can be continuous,discontinuous, woven, nonwoven, bundled etc and made of cotton,cellulose, nylon, polyester, aramid, glass, rayon or acrylic fibers orcords or mixtures of the same. It may be necessary in some instances totreat the fabric with an adhesive coating or dip to adhere or improveadhesion of the fabric to the vinyl chloride polymer composition.

The vinyl chloride polymer composition film or layer, supported orunsupported, is preferably printed on the surface with a suitable vinylchloride polymer receptive ink to form desirable and novel patternand/or design. Such inks are well known and can be applied by variousmethods of printing such as by gravure, flexography, screen printing,jet printing, web printing, non-impact printing and so forth as forexample, set forth in “Modern Plastics Encyclopedia 1980-1981,” pages464-465. The printing operation may be repeated for up to five times ormore to vary the colors and designs at temperatures of desirably fromabout 150 to about 165° F. (66-74° C.) for each printing step.

The vinyl chloride polymer composition film or layer, supported orunsupported, printed or unprinted, is preferably embossed to texture thevinyl chloride layer to provide a pattern or design for esthetic orfunctional purposes. Embossing of thermoplastic films, layers or sheetsis well known and is usually carried out by passing the film between anembossing roll and a backup roll under controlled preheating andpost-cooling conditions. See “Modern Plastics Encyclopedia 1980-1981,”pages 454-45. Additional decorating or printing can sometimes be donewith the above stated inks over the embossed vinyl chloride polymersurface for better aesthetic purposes.

The following examples will serve to illustrate the present inventionwith more particularity to those skilled in the art.

Preparation of Poly-Fox Materials (U.S. Pat. No. 5,650,483)

A 10 L jacketed reaction vessel with a condenser, thermo-couple probe,and a mechanical stirrer was charged with anhydrous methylene chloride(2.8 L), and 1,4-butanediol (101.5 g, 1.13 moles). BF₃THF (47.96 g,0.343 moles) was then added, and the mixture was stirred for 10 minutes.A solution of 3-Fox (3,896 g, 21.17 moles) in anhydrous methylenechloride (1.5 L) was then pumped into the vessel over 5 hours. Thereaction temperature was maintained between 38 and 42° C. throughout theaddition. The mixture was then stirred at reflux for an additional 2hours, after which ′H NMR indicated >98% conversion. The reaction wasquenched with 10% aqueous sodium bicarbonate (1 L), and the organicphase was washed with 3% aq. HCl (4 L) and with water (4 L). The organicphase was dried over sodium sulfate, filtered, and stripped of solventunder reduced pressure to give 3,646 g (91.2%) of title glycol, a clearoil. NMR: The degree of polymerization (DP) as determined by TFAAanalysis was 15.2 which translates to an equivalent weight of 2804. TheTHF content of this glycol, as determined by 1 H NMR, was 2.5% wt THF(6.2% mole THF). This was used in Examples I and II.

EXAMPLE I (COATING COMPOSITION)

Melamine resin (Resimene 747, 25.92 g) and polyester resin (Vr-248,Texas Resin, 74.78 g) were mixed with variable amounts of a Poly-Fox-3polymer available from Aerojet in Sacramento, Calif. Isopropyl acetate82.00 g and tetrahydrofuran (THF) 8.30 g were added to reduce theviscosity. A small amount of p-toluene sulfonic acid 39.6 g (10%solution in isopropanol) was added and the solution was mixed undershear for 5 minutes. Poly-Fox-3 polymer is a hydroxyl terminatedcopolymer including repeat units from an oxetane monomer wherein saidhydroxyl terminated polymer includes repeat units from an oxetane andrepeat units from tetrahydrofuran. having a pendant —CH₂—O—(CH₂)_(n)Rfgroup where Rf is CF₃.

EXAMPLE II

A smooth PVC film was coated with a solvent borne PVC/acrylate primer. Aportion of the primed substrate was coated with the composition ofExample I which had no Poly-Fox-3 (Example II Control) and a portion ofthe substrate was coated with the composition of Example I which had 2parts by weight of Poly-Fox-3 per 100 parts by weight total of saidpolyester and melamine resins, (Example IIA). The coatings on Example IIControl and Example IIA were cured at 200° F. (93° C.). Commercial dryerase markers were used to mark both examples. The resulting marks wereeasily removed with a dry cloth or eraser from Example IIA. The ExampleII Control erased partially but left severe shadowing using a dryeraser.

While in accordance with the patent statutes the best mode and preferredembodiment have been set forth, the scope of the invention is notlimited thereto, but rather by the scope of the attached claims.

What is claimed is:
 1. A laminate comprising: a substrate; and a stainresistant and adherent layer on said substrate comprising thecross-linked reaction product of at least; an amino resin cross-linkingagent and a reactive polyester resin including therein at least onerepeat unit derived from a hydroxyl terminated polymer including repeatunits from an oxetane having a pendant —CH₂—O—(CH₂)_(n)— Rf group , saidreactive polyester resin being formed by the prereaction of a diacidwith said hydroxyl terminated polymer including repeat units from anoxetane having a pendant —CH₂—O—(CH₂)_(n)— Rf group, and then in aseparate reaction adding a diacid and a polyol to the reaction productof said diacid with said hydroxyl terminated polymer and reacting thesame to form said reactive polyester resin, wherein said Rf group,independently, being a linear or branched alkyl group of 1 to 20 carbonatoms and a minimum of 25 percent of the hydrogen atoms of said alkylgroup being replaced by F, or said Rf group, independently, being aperfluorinated polyether having from 4 to 60 carbon atoms, and n beingfrom 1 to 3, and optionally up to 20 wt %, based on the weight of saidhydroxyl terminated polymer, of a cyclic tetramer from thepolymerization of an oxetane monomer having a pendant —CH₂—O—(CH₂)_(n)—Rf group wherein Rf is described above.
 2. A laminate according to claim1, wherein said Rf group independently is said linear or branched alkylgroup of from 1 to about 20 carbon atoms with a minimum of 85% of thehydrogen atoms replaced by F, wherein said diacid added in said separatereaction comprises adipic acid, azelaic acid, sebacic acid, terephthalicacid, or phthalic anhydride, or combinations thereof, and wherein saidpolyol comprises ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, or trimethylolethane, orcombinations thereof.
 3. A laminate according to claim 2, wherein thesurface of said substrate includes a layer of plasticized vinyl chloridepolymer.
 4. A laminate according to claim 2, wherein said substratecomprises a cellulosic product, fibers, synthetic polymers, metal orceramic.
 5. A laminate according to claim 2, wherein said Rf group hasfrom 1 to about 7 carbon atoms, and wherein said amino resin isalkylated benzoguanamine-formaldehyde, or an alkylatedurea-formaldehyde, or an alkylated melamine-formaldehyde, orcombinations thereof.
 6. A laminate according to claim 5, wherein saidhydroxyl terminated polymer includes repeat units from oxetanes andrepeat units from tetrahydrofuran.
 7. A laminate according to claim 5,wherein said stain resistant layer has the characteristic of beingeasily cleaned of undesired markings without using liquids.
 8. Acomposition, comprising; a crosslinked reaction product of at least anamino resin cross-linking agent and a reactive polyester resin includingtherein at least one repeat unit derived from a hydroxyl terminatedpolymer including repeat units from an oxetane having a pendant—CH₂—O—(CH₂)_(n)— Rf group, said reactive polyester resin being formedby the prereaction of a diacid with said hydroxyl terminated polymerincluding repeat units from an oxetane having a pendant—CH₂—O—(CH₂)_(n)— Rf group, and then in a separate reaction adding adiacid and a polyol to the reaction product of said diacid with saidhydroxyl terminated polymer and reacting the same to form said reactivepolyester resin, wherein said pendant —CH₂—O—(CH₂)_(n)— Rf group,independently, on different repeat units is a linear or branched alkylgroup of 1 to 20 carbon atoms, a minimum of 25 percent of the hydrogenatoms of said alkyl group being replaced by F, or said Rf group,independently, being a perfluorinated polyether having from 4 to 60carbon atoms, and n is from 1 to
 3. 9. A composition according to claim8, wherein said Rf independently is said linear or branchedperfluorinated alkyl group having from 3 to 10 carbon atoms, and aminimum of 85% of the hydrogen atoms replaced by F.
 10. A compositionaccording to claim 9, wherein said diacid added in said separatereaction comprises adipic acid, azelaic acid, sebacic acid, terephthalicacid, or phthalic anhydride, or combinations thereof, and wherein saidpolyol comprises ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, or trimethylolethane, orcombinations thereof.
 11. A composition according to claim 10, whereinsaid hydroxyl terminated polymer includes repeat units from oxetane andrepeat units from tetrahydrofuran.
 12. In an article including asubstrate having a protective coating thereon, the improvement whereinthe protective coating comprises a crosslinked reaction product of atleast an amino resin cross-linking agent and a reactive polyester resinincluding therein at least one repeat unit derived from a hydroxylterminated polymer including repeat units from an oxetane having apendant —CH₂—O—(CH₂)_(n)— Rf group, said reactive polyester resin beingformed by the prereaction of a diacid with said hydroxyl terminatedpolymer including repeat units from an oxetane having a pendant—CH₂—O—(CH₂)_(n)— Rf group, and then in a separate reaction adding adiacid and a polyol to the reaction product of said diacid with saidhydroxyl terminated polymer and reacting the same to form said reactivepolyester resin, wherein said pendant —CH₂—O—(CH₂)_(n)Rf groupindependently on different repeat units is a linear or branched alkylgroup of 1 to 20 carbon atoms and a minimum of 25 percent of thehydrogen atoms of said alkyl group being replaced by F, or said Rf,independently, being a perfluorinated polyether having from 4 to 60carbon atoms, and n being from 1 to
 3. 13. In an article according toclaim 12, wherein said Rf group independently is said linear or branchedalkyl group of from 1 to about 20 carbon atoms with a minimum of 85% ofthe hydrogen atoms replaced by F, wherein said diacid added in saidseparate reaction comprises adipic acid, azelaic acid, sebacic acid,terephthalic acid, or phthalic anhydride, or combinations thereof, andwherein said polyol comprises ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, or trimethylolethane, orcombinations thereof, and wherein said amino resin is alkylatedbenzoguanamine-formaldehyde, or an alkylated urea-formaldehyde, or analkylated melamine-formaldehyde, or combinations thereof.
 14. In anarticle according to claim 13, wherein the surface of said substrateincludes a layer of plasticized vinyl chloride polymer.
 15. In anarticle according to claim 13, wherein said substrate comprises acellulosic product, fibers, synthetic polymers, metal or ceramic.
 16. Inan article according to claim 13, wherein said hydroxyl terminatedpolymer includes repeat units from oxetanes and repeat units fromtetrahydrofuran.
 17. In an article according to claim 12, wherein asurface of said substrate has been printed or embossed, or a combinationthereof.
 18. A laminate comprising: a substrate, and a stain resistantand adherent layer on said substrate, comprising the cross-linkedreaction product of at least one amino resin cross-linking agent and areactive polyester resin and a hydroxyl terminated polymer includingrepeat units from an oxetane having a pendant —CH₂—O—(CH₂)_(n)— Rfgroup, said Rf group, independently, being a linear or branched alkylgroup of 1 to 20 carbon atoms and a minimum of 25 percent of thehydrogen atoms of said alkyl group being replaced by F, or said Rfgroup, independently, being a perfluorinated polyether having from 4 to60 carbon atoms, and n being from 1 to 3 and optionally, up to 20 wt %,based on the weight of said hydroxyl terminated polymer, of a cyclictetramer from the polymerization of an oxetane monomer having a pendant—CH₂—O—(CH₂)_(n)— Rf group wherein Rf is described above.
 19. A laminateaccording to claim 18, wherein Rf, independently, is a linear orbranched alkyl having from 1 to about 7 carbon atoms and a minimum of85% of the hydrogen atoms are replaced by F, wherein said reactivepolyester resin is derived from at least one diacid and at least onepolybasic alcohol, wherein said at least one diacid comprises adipicacid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride,and combinations thereof, and wherein said at least one polybasicalcohol comprises ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane, andcombinations thereof, and optionally wherein said hydroxyl terminatedpolymer includes repeat units from an oxetane and repeat units fromtetrahydrofuran.
 20. A laminate according to claim 19, wherein a surfaceof said substrate has been printed or embossed, or a combinationthereof.
 21. A laminate according to claim 19, wherein the surface ofsaid substrate includes a layer of plasticized vinyl chloride polymer.22. A laminate according to claim 19, wherein said substrate comprises acellulosic product, fibers, synthetic polymers, metal or ceramic.
 23. Alaminate according to claim 19, wherein said amino resin is alkylatedbenzoguanamine-formaldehyde, or an alkylated urea-formaldehyde, or analkylated melamine-formaldehyde, or combinations thereof.
 24. Acomposition comprising; a crosslinked reaction product of at least oneamino resin cross-linking agent and a reactive polyester resin and ahydroxyl terminated polymer including repeat units from an oxetanehaving a pendant —CH₂—O—(CH₂)_(n)— Rf group, wherein said pendant—CH₂—O—(CH₂)_(n)— Rf group, independently, on different repeat units isa linear or branched alkyl group to 1 to 20 carbon atoms, a minimum of25 percent of the hydrogen atoms of said alkyl group being replaced byF, or said Rf group, independently, being a perfluorinated polyetherhaving from 4 to 60 carbon atoms, and n is from 1 to
 3. 25. Acomposition according to claim 24, wherein Rf, independently, is alinear or branch alkyl having from 1 to about 7 carbon atoms and aminimum of 85% of the hydrogen atoms are replaced by F, wherein saidreactive polyester resin is derived from at least one diacid and atleast one polybasic alcohol, wherein said at least one diacid comprisesadipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalicanhydride, and combinations thereof, and wherein said at least onepolybasic alcohol comprises ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane, andcombinations thereof, and optionally wherein said hydroxyl terminatedpolymer includes repeat units from an oxetane and repeat units fromtetrahydrofuran.
 26. A composition according to claim 25, wherein saidhydroxyl terminated polymer includes repeat units from oxetanes andrepeat units from tetrahydrofuran, and wherein said amino resin isalkylated benzoguanamine-formaldehyde, or an alkylatedurea-formaldehyde, or an alkylated melamine-formaldehyde, orcombinations thereof.
 27. In an article including a substrate having aprotective coating thereon, the improvement wherein the protectivecoating comprises a crosslinked reaction product of at least one aminoresin cross-linking agent and a reactive polyester resin and a hydroxylterminated polymer including repeat units from an oxetane having apendant —CH₂—O—(CH₂)_(n)— Rf group, wherein said pendant—CH₂—O—(CH₂)_(n)Rf group independently-on different repeat units is alinear or branched alkyl group of 1 to 20 carbon atoms and a minimum of25 percent of the hydrogen atoms of said alkyl group being replaced byF, or said Rf, independently, being a perfluorinated polyether havingfrom 4 to 60 carbon atoms, and n being from 1 to
 3. 28. In an articleaccording to claim 27, wherein Rf, independently, is a linear orbranched alkyl having from 1 to about 7 carbon atoms and a minimum of85% of the hydrogen atoms are replaced by F, wherein said reactivepolyester resin is derived from at least one diacid and at least onepolybasic alcohol, wherein said at least one diacid comprises adipicacid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride,and combinations thereof, and wherein said at least one polybasicalcohol comprises ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane, andcombinations thereof, and optionally wherein said hydroxyl terminatedpolymer includes repeat units from an oxetane and repeat units fromtetrahydrofuran.
 29. In an article according to claim wherein a surfaceof said substrate has been printed or embossed, or a combinationthereof.
 30. In an article according to claim 28, wherein the surface ofsaid substrate includes a layer of plasticized vinyl chloride polymer.31. In an article according to claim 28, wherein said substratecomprises a cellulosic product, fibers, synthetic polymers, metal orceramic.
 32. In an article according to claim 28, wherein said aminoresin is alkylated benzoguanamine-formaldehyde, or an alkylatedurea-formaldehyde, or an alkylated melamine-formaldehyde, orcombinations thereof.